CN113061921B - Porous carbon loaded TiN-Pt water decomposition hydrogen production electrocatalyst and preparation method thereof - Google Patents
Porous carbon loaded TiN-Pt water decomposition hydrogen production electrocatalyst and preparation method thereof Download PDFInfo
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- CN113061921B CN113061921B CN202110273780.7A CN202110273780A CN113061921B CN 113061921 B CN113061921 B CN 113061921B CN 202110273780 A CN202110273780 A CN 202110273780A CN 113061921 B CN113061921 B CN 113061921B
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Abstract
The invention discloses a porous carbon loaded TiN-Pt catalyst for hydrogen production by high-efficiency electrocatalysis water decomposition and a preparation method thereof. The method comprises the following steps: and (2) taking metal organic framework Materials (MOFs) as precursors, calcining at high temperature to obtain a TiN carrier loaded with porous carbon, adsorbing the anionic Pt salt onto the surface of TiN by the adsorption action of a cationic surfactant, and further roasting to obtain the target catalyst. The raw materials are cheap and easy to obtain, the catalyst can be prepared in a large scale, the electronic structure of Pt is modified by the interaction between TiN and Pt, and finally the catalyst shows high-efficiency electrocatalytic water decomposition hydrogen production performance. At a Pt content of only 1.23%, the current density was 10mA cm ‑2 The overpotential required was only 35mV, far better than 20% of commercial Pt electrocatalysts.
Description
Technical Field
The invention belongs to the field of nanotechnology and the field of electrocatalysis, and particularly relates to a preparation method of a porous carbon-loaded TiN-Pt catalyst and application of the porous carbon-loaded TiN-Pt catalyst in the field of electrocatalysis hydrogen production.
Background
In recent years, global energy demand has been increasing, fossil fuels have been gradually exhausted, global environment has been deteriorating, and green renewable energy sources such as wind energy, geothermal energy, solar energy, and the like have been urgently developed. However, the supply of these sustainable energy sources is usually intermittent, depends on geographical, seasonal and weather conditions, and has temporal and spatial differences between supply and demand. Therefore, in order to realize the utilization of renewable energy, there is a need for the development of energy conversion and storage technologies, such as water decomposition capable of converting electric energy generated by solar energy and wind energy into hydrogen fuel, and a rechargeable metal air battery, which have the characteristics of high energy density, low cost, environmental friendliness, high safety, and the like, and a Reversible Fuel Cell (RFC) can also produce hydrogen fuel through an electrochemical process. However, the slow kinetics of the Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) severely hamper the development of energy conversion and storage systems, as controlled by the electrochemical reaction conditions.
In order to solve the above problems, we must select a suitable catalyst to improve the energy conversion efficiency. At present, noble metal catalysts are still the most effective catalysts of HER and OER, wherein Pt is the most excellent HER catalyst, but the defects of high price, rare reserves, uneven distribution, instability in the catalytic process and the like greatly limit the wide application of Pt-based catalysts. Therefore, reducing the amount of Pt used and selecting a suitable support substrate to improve the stability thereof are important directions for improving the catalytic performance of Pt-based catalysts, and are major components for developing economically efficient water electrolysis systems. To date, a variety of HER catalysts, abundant in reserves and having significant catalytic activity, have been reported in the literature, including Transition Metal Dihalides (TMDs), transition Metal Phosphides (TMPs), transition metal carbides and nitrides, and the like. Among them, transition metal nitrides have attracted much attention by virtue of their unique electronic structures, higher electrical conductivity, and excellent chemical stability and mechanical strength.
Among many transition metals, metallic titanium is one of the most abundant elements on earth, and nitrides thereof have remarkable characteristics of high hardness, high thermal conductivity, good stability and the like. Because of its properties similar to those of noble metals, tiN has been widely used in the fields of electrocatalysis (electrocatalytic water decomposition), electrochemical energy storage (various batteries, supercapacitors) and energy conversion (fuel cells and solar cells), and has high catalytic activity and stability under acidic, alkaline and oxidative environments and the like. In addition, we can easily control the morphology and structure of TiN. Therefore, in summary, tiN is a good substrate material, and the synergistic effect between TiN and the noble metal is also beneficial to improving the catalytic performance.
The invention aims to improve the catalytic performance of the catalyst on the basis of reducing the consumption of noble metal Pt, designs an efficient porous carbon supported TiN supported Pt nanoparticle catalyst, and can realize the efficient catalytic performance by using extremely low noble metal content.
The purpose of the invention is realized by at least one of the following technical schemes:
the preparation method of the porous carbon loaded TiN-Pt high-efficiency electrocatalytic water-splitting hydrogen production catalyst provided by the invention comprises the following steps:
(1) Preparing a porous carbon loaded TiN precursor: NH (NH) 2 Synthesis of MIL-125: dropping tetrabutyl titanate into the clear solution of 2-amino terephthalic acid, stirring and then transferringMoving the reaction kettle to a high-temperature reaction kettle, and placing the reaction kettle in a drying oven for heating reaction to obtain NH 2 -MIL-125 yellow powder. Reacting NH 2 And roasting MIL-125 at high temperature in an inert atmosphere to obtain the porous carbon loaded TiN precursor.
(2) Adding soluble Pt salt into TiN dispersion liquid containing cationic surfactant, stirring, centrifuging, washing, drying, and then calcining at high temperature under inert atmosphere to obtain the porous carbon loaded TiN-Pt electrocatalyst.
Further, step (1) of said NH 2 -MIL-125 is a microparticle having a particle size of 1-10 μm.
Further, step (1) of said NH 2 -the calcination temperature of the MIL-125 is 800-1100 DEG C
Further, the TiN in the step (2) is micron particles with the particle size of 1-10 μm.
Further, the soluble Pt salt in the step (2) is potassium tetracyanoplatinate, chloroplatinic acid, potassium chloroplatinate and the like, and the mass is 2-6mg.
Further, the solvent used in step (2) is methanol, ethanol or deionized water.
Further, the stirring time used in the step (2) is 2-5h.
Further, the centrifugal rotating speed used in the step (2) is 6000-10000rpm/min, and the washing times are 3-6 times.
Further, the drying time used in the step (2) is 3-8h, and the drying temperature is 60-90 ℃.
Furthermore, the calcining temperature used in the step (2) is 500-1000 ℃, and the calcining time is 1-3h.
Further, the inert gas used in the step (2) is nitrogen or argon.
Preferably, the roasting temperature in the step (2) is 700 ℃, and the roasting time is 2h.
The invention provides a TiN-Pt high-efficiency electrocatalytic water decomposition hydrogen production catalyst prepared by the preparation method
The method takes TiN as a carrier and Pt salt as a precursor of Pt, and the Pt is adsorbed on the surface of the TiN by adding a surfactant; and roasting to obtain the catalyst.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the high-efficiency electro-catalytic hydrogen production TiN-Pt catalyst prepared by the invention has the advantages of easily obtained raw materials and simple process, the defect-rich TiN which is prepared by roasting MOFs as a precursor in an inert atmosphere is used for anchoring Pt atoms, and the load capacity of Pt is only 1.23%. The TiN-Pt has excellent catalytic performance in an electro-catalytic hydrogen production system, and the current density of 10mA cm can be reached only by 35mV -2 Better than commercial Pt/C (20%).
Description of the drawings:
FIG. 1 is a PXRD pattern for TiN and TiN-Pt.
Fig. 2 is an SEM image of TiN.
FIG. 3 is an SEM image of TiN-Pt.
FIG. 4 is a graph showing hydrogen production performance of an electrocatalyst.
Detailed Description
The following examples are included to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all implemented or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be commercially available products.
Example one
(1) 0.21 g of 2-aminoterephthalic acid was weighed out and dissolved in 7mL of CH 3 Stirring the mixed solution of OH and 3mLDMF for 1h at room temperature, transferring the mixed solution to a 25mL reaction kettle, reacting for 12h at 130 ℃, washing, centrifuging and drying to obtain NH 2 -MIL-125 yellow powder. Reacting NH 2 -MIL-125 is placed in a tube furnace for high temperature calcination with a heating rate of 5 ℃/min, N 2 Calcining at 1050 ℃ for 3h in the atmosphere to obtain black TiN powder.
(2) Uniformly dispersing TiN powder in 10mL CH 3 OH and 20mL H 2 And adding 36mg of hexadecyl trimethyl ammonium bromide into the mixed solution of O, stirring for half an hour, adding 3mg of potassium tetracyanoplatinate, stirring for 3 hours, washing, centrifuging and drying to obtain TiN-Pt precursor powder. Putting TiN-Pt precursor powder into a tube furnace for high-temperature calcination,the heating rate is 5 ℃/min, N 2 Calcining for 2h in the atmosphere to obtain black TiN-Pt powder.
The XRD pattern of the catalyst prepared in example 1 is shown in fig. 1. As can be seen from FIG. 1, the addition of Pt did not shift the XRD peak position of TiN, indicating that Pt was not incorporated into the crystal lattice of TiN, and no diffraction peak of Pt was observed in the XRD of TiN-Pt, indicating that the content of Pt was small. Scanning electron microscopes of TiN and TiN-Pt are respectively shown in fig. 2 and fig. 3, and the morphology of TiN is not changed in the Pt loading process.
The catalyst prepared in example 1 is used for carrying out an experiment of hydrogen production by electrocatalytic water decomposition on water, and the electrolyte is 1 MH 2 SO 4 The silver/silver chloride electrode is a reference electrode, the platinum sheet electrode is a counter electrode, and the catalysis result is shown in fig. 4. As can be seen from FIG. 4, tiN-Pt only requires 35mV of overpotential to reach 10mA cm -2 Current density of (2), whereas commercial Pt/C (20%) requires 45mV to reach 10mA cm -2
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (7)
1. A preparation method of a porous carbon loaded TiN-Pt electrocatalytic water decomposition hydrogen production catalyst is characterized by comprising the following steps:
(1) Roasting Ti-based MOFs at high temperature to obtain a porous carbon-loaded TiN substrate, uniformly dispersing the substrate into a solvent, adding a cationic surfactant and soluble Pt salt, stirring, centrifuging, washing and drying to obtain a porous carbon-loaded TiN-Pt precursor;
(2) Calcining the precursor synthesized in the step (1) in an inert atmosphere to obtain the high-efficiency porous carbon loaded TiN-Pt electro-catalytic hydrogen production catalyst, wherein the loading amount of Pt is only 1.23%;
adding 2-6mg of soluble Pt salt used in the step (1), wherein the calcining temperature of Ti-based MOFs is 800-1100 ℃; porous carbon loaded TiN precursor composed of NH 2 -MIL-125 synthesis;
the calcining temperature of the porous carbon loaded TiN-Pt precursor in the step (2) is 500-1000 ℃.
2. The preparation method of the porous carbon supported TiN-Pt high-efficiency electrocatalytic hydrogen production catalyst according to claim 1, wherein the Ti-based MOFs in the step (1) are micron-sized particles with a particle size of 1-10 μm.
3. The preparation method of the porous carbon-supported TiN-Pt high-efficiency electrocatalytic hydrogen production catalyst as claimed in claim 1, wherein the TiN substrate in the step (1) is micron-scale particles with the particle size of 1-10 μm, and the used surfactant is a cationic surfactant.
4. The preparation method of the porous carbon-supported TiN-Pt high-efficiency electro-catalytic hydrogen production catalyst according to claim 1, characterized in that the stirring time used in the step (1) is 2-5h, the centrifugal rotation speed used is 6000-10000rpm, and the washing times are 3-6 times.
5. The preparation method of the porous carbon-supported TiN-Pt high-efficiency electro-catalytic hydrogen production catalyst according to claim 1, characterized in that the drying time used in the step (1) is 3-8h, and the drying temperature is 60-90 ℃.
6. The preparation method of the porous carbon supported TiN-Pt high-efficiency electrocatalytic hydrogen production catalyst according to claim 1, wherein the inert gas used in the step (2) is nitrogen or argon.
7. A highly efficient electrocatalytic hydrogen production catalyst from porous carbon-supported TiN-Pt prepared by the preparation method according to any one of claims 1 to 6, wherein hydrogen gas is produced in an electrified state.
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